Polymeric antifoggant containing at least four triazine rings

ABSTRACT

A photographic silver halide light-sensitive element illustrating a marked reduction in fog which has a layer which contains a compound having a repeating unit represented by the following formula:   The specific moieties symbolically represented in the above formula are defined in the specification. The active antifoggant illustrated above may be incorporated into a silver halide emulsion layer, a protective layer and in intermediate layer or the like.

United States Patent Inventors Fumihlko Nlshio;

Nobuo Yamamoto; Jun llayashi, all of Mlnami-Ashigara Machi, Ashigara- POLYMERIC ANTIFOGGANT CONTAINING AT LEAST FOUR TRIAZINE RINGS 8 Claims, No Drawings US. Cl

Int. Cl

Field of Search References Cited UNITED STATES PATENTS 7/ 1962 Carroll et a] 96/109, 96/ l 14 G03c 1/34, G030 1/72 96/ 109 FOREIGN PATENTS 1,150,279 6/l963 Germany Primary ExaminerNorman G. Torchin Assistant Examiner-Richard E. F ichter Attorney-Sughrue, Rothwell, Mion, Zinn & Macpeak ABSTRACT: A photographic silver halide light-sensitive element illustrating a marked reduction in fog which has a layer which contains a compound having a repeating unit represented by the following formula:

The specific moieties symbolically represented in the above formula are defined in the specification. The active antifoggant illustrated above may be incorporated into a silver halide emulsion layer, a protective layer and in intermediate layer or the like.

POLYMERIC ANTIFOGGANT CONTAINING AT LEAST FOUR TRIAZINE RINGS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an improved photographic silver halide light-sensitive element containing an antifoggant.

2. Description of the Prior Art By incorporating in a photographic silver halide emulsion a natural active gelatin, a compound having labile sulfur, a noble metal salt, a heavy metal salt, reducing agents such as an amine, a hydrazine, or a polyalkylene oxide derivative, or combinations thereof, the sensitivity of the silver halide emulsion can be increased. However, fog tends to increase with the addition of such compounds. This tendency is increased as the period of time for storing photographic light-sensitive elements becomes longer, or the temperature and humidity during storage are increased.

in order to prevent the formation of fog, it is necessary to use an antifoggant. Aging tests have usually been conducted to test the preservability of photographic light-sensitive elements under high temperature and high humidity. It is desirable that photographic light-sensitive elements be as stable as possible under high temperature and high humidity conditions, as these are frequently encountered in the tropics.

SUMMARY OF THE lNVENTlON it has been found that a photographic light-sensitive element in which the formation of fog may effectively be prevented without a reduction in sensitivity may be obtained by the incorporation in a silver halide layer, a protective layer and an intermediate layer or the like, of a compound which contains a repeating unit represented by the following formula:

wherein R represents a member selected from the group consisting of OR,

fj ,r where R and R'each represent a member selected from the group consisting of (i) a hydrogen atom; (ii) an alkyl group having from one to 12 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from one to four carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from six to 12 carbon atoms, an aryl group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom; an unsubstituted cycloalkyl group, and a cycloalkyl group substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, each of said cycloalkyl groups having from three to six carbon atoms, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom; and (iv) a heterocyclic group; A represents a member selected from the group consisting of a polymethylene group having from four to five carbon atoms, and a polymethylene group having a heteroatomic group and forming a five to six membered ring together with a nitrogen atom; R R R,, and R each represent a member selected from the group consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms and a hydroxyalkyl group; Y Y Y and Y each represent a member selected from the group consisting of a polymethylene group having from two to 12 carbon atoms, a polymethylene group having from two to 12 carbon atoms substituted by a member selected from the group consisting of an alkyl group having from one to four carbon atoms and a hydroxyalkyl group having from one to four carbon atoms, an arylene group having six to 12 carbon atoms, an arylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, a cycloalkylene group having from six to 12 carbon atoms, and a cycloalkylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a ,carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having one to four carbon atoms and a halogen atom; 2 represents a member ,selected from the group consisting of a divalent heteroatom, a divalent heteroatomic group, and a hydrocarbon residual group having from one to two carbon atoms; and k and m each represents 0 or 1.

When the compound shown above is present in the silver halide emulsion layer, it is preferred that it be present in amounts from about 0.0] g. to about 50 g./ l mole of silver halide in the emulsion. When the compound shown above is added to a protective layer, it is preferred that the compound be present in amounts from about 0.05 g. to about 250/ 1 kg. of I gelatin in the layer. When the compound shown above is added to an intermediate layer, it is preferred that the compound be present in amounts from about 0.05 g. to about 250 'g./ l kg. of gelatin in the layer.

A number of specific examples of the compound utilized in the present invention are set out in the specification, and vari- .ous acceptable methods of forming the compound of the present invention are also illustrated therein.

An object of this invention is to provide a photographic light-sensitive element in which the formation of fog is effectively prevented without a reduction in sensitivity.

Another object of this invention is to provide a photographic light-sensitive element which can be stored for a long :period of time without the formation of fog and which will remain stable during storage.

Still another object of this invention is to provide a photographic emulsion having a good preservability, that is, one which will illustrate less degradation in sensitivity and contrast ,when preserved for a long period of time.

A still further object of this invention is to provide a photographic light-sensitive element in which the formation of fog, caused when the photographic silver halide emulsion layer is processed in a formalin-containing bath before developing in order to preliminarily harden the gelatin film, is prevented without lowering the sensitivity of the light-sensitive photographic element.

To prevent the formation of fog in photographic light-sensitive elements it has been found that the objects of this invention can be attained by incorporating in a photographic layer 'of a photographic light-sensitive element, having a silver halide emulsion layer, an antifoggant having a repeating unit represented by the following general fonnula l):

OR, sn, N/ and N A where R and R each represents a member selected from the group consisting of (i) a hydrogen atom: (ii) an alkyl group having one to l2 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from one to four carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from six to 12 carbon atoms, an aryl group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxy group, a salt thereof, a hydroxyl group, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom; an unsubstituted cycloalkyl group, and a cycloalkyl group substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, each of said cyloalkyl groups having from three to six carbon atoms, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms, and a halogen atom; and (iv) a heterocyclic group; A represents a member selected from the group consisting of a polymethylene group having from four to five carbon atoms, and a polymethylene group having a heteroatomic group and forming a fiveto six-membered ring together with a nitrogen atom; R R,,, R, and R, each represent a member selected from the group consisting of a hydrogen atom, an alkyl group having from one to four carbon atoms and a hydroxyalkyl group; Y,, Y Y and Y each represent a member selected from the group consisting of a polymethylene group having from two to 12 carbon atoms, a polymethylene group having from two to 12 carbon atoms substituted by a member.

selected from the group consisting of an alkyl group having from one to four carbon atoms and a hydroxyalkyl group having from one to four carbon atoms, an arylene group having from six to 12 carbon atoms, an arylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom, a cycloalkylene group having from six to 12 carbon atoms, and a cycloalkylene group having from six to 12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from one to four carbon atoms, an alkoxy group having from one to four carbon atoms and a halogen atom; 2 represents a member selected from the group consisting of a divalent heteroatom, a divalent heteroatomic group and a hydrocarbon residual group having from one to two carbon atoms; k and m each may represent or 1; R may be same as R R may be same as R Y, may be same as Y and Y may be same as Y.,.

The antifoggant used in the present invention is a high molecular compound having s-triazine rings prepared by the method described below.

Although there is no particular restriction about the distribution of polymerization degree, based on the viscosity of a solution of the antifoggant or the number of the terminal groups of said compound, the main component of the antifoggant is considered to be composed of a polymer having more than four s-triazine rings in the main chain.

The aforesaid antifoggant having a repeating unit represented by general formula (I) described above may be prepared by the polycondensation reaction of a s-triazine compound repr esented bygeneral formula H [wherein X represents a halogen atom such as a chlorine atom or a bromine atom, R, has the same meaning described in connection with general formula (l)]and a diamino compound, represented by general formula (III) or (IV) [wherein R R;,, R,, R Y,, Y Y Y,, Z, k, and m have the same meaning as described in connection with general formula (1)] or by the polycondensation reaction of a bis-( halogenos-triazine) compound represented by general formula (V) or [wherein X has the same meaning described in connection with general formula (II) and R,, R R R, R Y Y2, 3, 4, Z, k and m have the same meaning as described in connection with general formula (1)] and the aforesaid diamino compounds represented by general formula (III) or (IV).

The halogeno-s-triazine compounds represented by general formulas (II), (V) and (VI) described above may be prepared from cyanuric chloride by the method described in the Journal of the American Chemical Society"; Vol. 73, 2981-2992 195 l The antifoggants used in this plained in greater detail.

Examples of R, aforesaid formulas (ll), (V) and (VI), may be as follows:

invention will now be exgeneral formula (I) and general illustrating the starting materials,

COONB S 03K CH CHgOI-I NHCH;CH;CHOH, N NHOH2OHZ SO3Na,

CH2CH2OH NHCH2CH;S O H,NHCHZC O OH 5 S K H 111-, 1

s OaNa 01 I0 @(0,m, ,m,

Cm H 111-. l

0 CH: C O 0 Ca ,m-.p). NH ,m.pt *7. A an". a.

SOaNH (CzHQaHNOaS- N. -NH- 1 r, Y N,

As examples of the groups 1 l a 5h N(YrZ) k-Y,N and N(YgZ)mY4 it V tt. 77 %J V e which occur in the compounds represented by general formulas (III), (IV), (V) and (VI), which are the starting materials for the antifoggant represented by general formula (I), or the reagents in the polycondensation for preparing the antifoggant of this invention, are illustrated as follows: 40

The preparation of the antifoggant having a repeating unit represented by general formula (I) described above may be prepared by the following two illustrative general methods.

a. About 1 mole of the dihalogeno-s-triazine compound represented by general formula (II) is reacted with 1 mole N Hz H20 Hz H2NH-, HN H2 H 2N 4 5 of the diamino compound represented by general formula H (ill) or (IV) in a suitable solvent, preferably water, CH3 acetone, dioxane, dimethylformamide, or diethylformamide at a proper temperature, e.g., at about lO-l C., EN OHPNH HN OH2 E OH2 NH with or without a suitable base preferably an alkali bicar- Ha H! 50 bonate, an alkali carbonate, a caustic alkali, or an organic CH8 base, e.g., pyridine, 2,4,6-trimethylpyridine, and diamino- HN-OH OHz-(JCH;OHzNH-, HN-(OH,) -N i y n n b. About 1 mole of the bis(halogeno-s-triazine) compound H H O OH 8 2 H2 represented by general formula (V) or (VI) described above is reacted with one mole of the diamino compound E (3H3 E E represented by general formula (III) or (IV) at a suitable -N-(CH2)2N, N(CH-.);-N NH temperature (preferably 30-l 50 C.) in the solvent and, if

desired, in the presence of a base as stated in method (a) The antifoggant of the present invention may, of course, be CHFCH prepared by methods other than those described above. Typical examples of a compound having a repeating unit HN-C represented by general formula (I) or (II) are illustrated 0H3 GHQ-CH2 CH3 below: The number of s-triazine rings The number of S-triazine rings Com ound 1 N p LK TNH(CH2MNHJ T wm .1

N L L \l/ NHCHzCHzOH NHCHzCHzOH Compound 2 n24 I NH? 93??? Com ound 14 N N n 4 p -W \1-NH(CH);NH4( NH(CH2)sNH NHCHzCHzSmNa Nrromoms O Na Corn ound15 N N n 4 p -NH(CH2)z-NH TNH(CH2)1oNH N L N I NHCHZCHQSOQH Nnomcmsoarr Com ound 16 N N 1124 p -f TNH- CHm-NH W *NH(CH2)4NH 1 \/LI N N Y NH-SO3N11 NH- SOaNa Compound 17 KNWNHNH(N\ NH-NH NH- NH S OBNB S OaNa Compound 18 N N n24 J WNH(CH2)3NH-( TNmomFNH l J N I V NH NH- S Na -S0 Na Com 0und19 F N N n 4 l IlQ'OH2CH2SO Na N-cmomsoma CzHs 2H5 Compound 20 F N N n24 w-NH 0H, 3NH Tmnonm-mr N\/ N lv Y N N The above compounds may generally be prepared by method (a) or (b) described above by specific examples of methods of preparation of compound 1 and compound 2 will be described below.

Preparation of compound l (method a):

368 g. of cyanuric chloride dissolved in 1.1 liters of acetone was gradually added to 1.5 liters of water, cooled to a temperature lower than C., with stirring. While further stirring the mixture at a temperature lower than 5 C., a solution consisting of 122 g. of ethanol amine, 212 g. of sodium bicarbonate and 800 ml. of water was added to the mixture over a 1.5 hour period. After additional stirring for 2 hours at the same temperature, the temperature of the mixture was gradually raised to about C. The system was further stirred for an additional 1 hour at this temperature. Crystals precipitated, and were recovered by filtration and subsequently recrystallized from water containing a small amount of sodium bicarbonate to yield 253 g. of 2,4-dichloro-6-(2- hydroxyethylamino)-s-triazine. The product was a white crystal having a melting point of 1 17] 19 C. (decomposed).

The 2,4-dichl0ro-6-(-2-hydroxyethylamino)-s-triazine (209 g.) obtained was mixed with 2 liters of water and while stirring the mixture at a temperature of 2025 C., a solution consisting of 70 g. of 1,3-diaminopropane and 300 ml. of water was added to the mixture over a one hour period. Thereafter, the temperature of the system was elevated to 3035 C. and a solution consisting of 168 g. of sodium carbonate and 1 liter of water was added to the mixture over a 40-minute period. After the addition thereof, the temperature of the system was elevated gradually and stirred for 3 hours at 100 C. The reaction mixture was filtered after being allowed to cool, and the product thus recovered was washed with water, until the washings became neutral, and dried to provide 200 g. of the white powders of compound 1. The intrinsic viscosity of compound measured in dimethylformamide at 35 C. was 0.104.

Preparation of Compound 2 (method b):

A mixture of 250 g. of 2,4-dichloro-6(2-hydroxyethylamino)-s-triazine (prepared by the method described above,) 2liters of acetone and 1 liter of water was stirred at 20 C. After adding a solution consisting of 40.7 g. of 1,3-

diaminopropane and 200 ml. of water to the mixture over a k Compound I6 8 30-minute period, a solution consisting of 10] g. of sodium 'g Z carbonate and 1 liter of water was added thereto over a 30- 3,2223 9 minute period. After completing the addition, the temperature 0 4-Hydroxy-6-methyl-l.3,3.a.7 of the system was raised to 40-45 C., and the system was 4euw'mindene stirred for 1 hour. The reaction mixture was then ice-cooled P i'2'gggz jzz gg fsgf A 5' and filtered to provide 232 g. of a white crystal. The product f 2 '4 'Dihydr1,yjsulfiethylaminmg was recrystallized from a dioxane-water 1:] mixed solution to triazine 0 5.0 provide 184 g. of the white crystal of l,3-bis(2'-chloro-4'- 5 i hydroxyethylamine-s-triazine-6-ylamino)-propane, having a I gg 'z gjg gf' 0 melting point (decomposed) of 276 C. hydroxyethylamino) A mixture of 42.5 g. of the l,3-bis(2'-chloro-4 hydroxy l 0 yethylamino-s-triazine-6'ylamino) propane thus obtained and u "23 0) S l iazinc 2 mine] n I -a 400 ml. of water was stirred at 30-35 C and after adding a z j acid 0 M solution consisting of 7.4 g. of ethylenedlamme monohydrate Control (no antifoggant) o 5.0 and 30 ml. of water to the mixture, the temperature of the Th f h I d h M d o e concentration 0 t e materia use in t e measurement was measure y a rFsultmg f was elevated C' Thereafter a Solu ding 1.6 ml. of a lpercent solution of each sample to 75 ml. of the test solution tron consisting of 16.8 g. of sodium bicarbonate and 120 ml. of (correspondingm Q34 B, f ABNQ1 water was added to the mixture over a 30-minute period. A b f th b tab! d f The temperature of the system was further elevated to 5 may i seen. mm 8 a y compoun s 0 90 95 C and heated and Stirred for 3 hours The reaction the present invention show physical retardance values in the mixture was then cooled to room temperature, filt r d, range d ypz fi d gmerizpltol-g-% ;e y;t:;a:;:dea:e washed with water and dried to provide 40 g. of the white pi b k y Oxy- T ts o powders of compound 2. The intrinsic viscosity of the product W are 0 as exce en an lg in dimuhylformamide measured at was 0.125. molecular compounds (p-ushown above), which are similar to Compounds 1 are shown above as typical exam the antifoggants of this invention in that they have one or two ples of the antifoggams used in this invention may be s-triazine rings, show a very weak physical retardance or lack prepared by methods similar to those illustrated for preparing of physlcal retardaxpe' compound I and compound 2. To illustrate the excellent anh f Size? of the hlgh molecular annfoggam used tifogging effect of the antifoggant of this invention, the physii f i fi words g g f n ofbthe cal retardance of the antifoggant of this invention compared' "i F con ame m compoun S wl now e exwith that of known antifoggant is shown in the table below. in Flamed m greater detml' Although these high 'Q anthis table, the physical retardance value was observed by con- 3" may be Prepared by the methods dcscvbed ventional physical retardance measuring methods for testing products prpzired by the polycondensaf'on, macho the chemical properties of photographic gelatin e.g., Testing of a compound and 3 3 for Photographic Gelatin (PAGI method); Commission pound are obtained as a mixture of polymers having different Testing Method for Photographic Gelatin (Japamn 1243 distributions of polymerization degree, depending upon reac- (1964) Specifically the measurement was pcrformed as in non conditions, such as reaction time, reaction temperature, the PA'GI method w'ith the exception that each of the reaction solvent, the catalyst, if one is used, and the mole ratio pounds was added to men gelatin and employed as the 40 of the dlhalogeno-s-tnazme compound to the dtammo comple. This measurement has been widely used, in view of the s f d h fact that the retardance in the 2nd ripening is proportional to as been however at products the physical retardance of the silver halide particle growth. tamed Show rema'kaPle Pracncal mem for use as The numeral 10 in the table represents the maximum regamsj basefi on expenmemal 9 only when the Q F tardance, and the numeral 0 represents a sample having no ini mamly of "P} f more than four stm 1zme hibmng properties. rings as the repeating unit. To illustrate, each conventional control compound (compounds v-z) which have one or two 5- Physicfll PH triazine rings, and compound l(n=4 or 1 l) of this invention, 'f Mmurcmem were added to a silver iodo-bromide high speed negative emulsion, which has been sulfur-sensitized and gold-sensitized. The 11 Compound I 9 antifogging effect and the physical inhibitance were then meal g 2 2'3 sured and the results are shown in the following table. d comznund 4 a 49 From the results of the above experiment, it was found that c Compound 9 7 4.8 while the conventional compounds illustrated, at best, a very f Compound I0 7 weak antifogging effect, compound l,which is an example of Cmnpmmd a 5D the antifo ant of the resent inventi n shows a ver st h Compound l3 9 4.8 g p 0 rong i compound 9 49 antifogging effect when the number of s-tnazlne rings was j Compound 15 I 4.8 four, as well as when the s-triazine rings numbered 1 1.

Concentration, Relation Physical Compound g./Ag 1 mol sensitivity Fog inhibitanee v N 2.0 97 0.16 0 (ll-f T01 4.0 96 0.17

a NHCzH4OH w N 2. 0 97 0. 17 0 o1- W-NHCzHlOH 4.0 98 0.16

H/ ll-101102114011 4.0 00 0.17} 0 Ngozmon N N 2.0 98 0.17 y HOT W'NHwHm-NHZF Ton 4.0 07 0.11} 0 V I Nnolnlon NHCQHlOH N N 2.0 00 0.10 z 01f TNH(OH)0NH I 01 4.0 95 0.15} 1 V l I NHC2H4OH Nncznlon 1n=4 N N 2.0 00 0.12

( Cl f WNH(CH2)aNH |r fi0l 4.0 98 0.08} 8 V l I NHCzH4OH 3 NHC2H4OH 2n=11 P N N 2.0 as 0.00 9

( 01- |-NH 0H)3NH W o1 4.0 01 0.00}

l IIIHC2H4OH 10 Nnolnlon Control (none) The intrinsic viscosity [1 of compound 1 measured in DMF i (F4) or 1 l) at C., and the values of elementary analysisl thereof, were as follows:

The compound, having the repeating unit shown by general formula (I), used in this invention shows an excellent antifogging effect or stabilizing power for photographic silver halide light-sensitive elements, and does not harmfully influence any other useful photographic properties.

The compounds of the invention may be used alone (or as mixtures thereof) as antifoggants or stabilizers. In addition, they may be used in combination with conventional antifoggants.

The antifoggants of this invention may be added to the silver halide emulsion at stages before the emulsion is applied to a support, but is preferably added between after-ripening and coating. Further, it has been found that the antifoggant of this invention can be very effectively incorporated in a photographic layer other than the silver halide emulsion layer, such as, a protective layer other than the silver halide emulsion layer, such as, a protective layer adjacent the silver halide emulsion layer or an intermediate layer between silver halide emulsion layers. In addition, since these compounds are dissolved in solvents such as water, dimethylforrnamide, dimethyl sulfoxide, water containing an acid (inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid, etc. or organic acids such as acetic acid) or water containing an alkali (such as acid alkali carbonate, an alkali carbonate, or an alkali hydroxide), it is often desirable to add the antifoggant compound in the form of a solution in the aforesaid solvents.

There is no particular limit to the concentration of the antifoggant of this invention which may be used, but a suitable concentration is generally 0.01-50 g. per 1 mole of silver haand 0.05-250 g. per 1 kg. of gelatin when adding it to a protective layer or to an intermediate layer. 7

The present invention is applicable to black and white negative emulsions, X-ray emulsions, the so-called coupler-inemulsion-type color photographic silver halide emulsions,

wherein a color coupler is incorporated in the emulsion, and the so-called coupler-in-developer-type color photographic silver halide emulsion, wherein a color coupler is incorporated in the developer. Improved results can be obtained when it is applied to a gelatino silver iodo-bromide emulsion. However, the invention is applicable to various other types of silver halide emulsions.

A silver halide emulsion containing the antifoggant of this invention may be chemically sensitized by conventional methods, such as by the addition of a compound containing a labile sulfur, e.g., ammonium thiosulfate and allylthio urea (of, if necessary, The Theory of the Photographic Process"; 3rd edition, 1 13-1 16 (1966); McMillan Company, New York); a complex salt of monovalent gold and thiocyanic acid (ibid., page l 16) reducing sensitizers, such as amines, hydrazines or a heavy metal salt such as stannous chloride (ibid.; pages ll31l6); and polyalkylene oxide derivatives, or combinations thereof. The emulsion used in this invention may further contain an inorganic hardening agent (ibid., page 55); or an organic hardening agent (ibid., pages 55-60). Moreover, the silver halide emulsion in this invention may contain a wetting agent, for example, a nonionic surface active agent, such as polyoxyethylenenonylphenyl ether; an anionion ,surface active agent such as sodium alkylbenzene sulfonate or ;sodium N-alkanoxyl-N-alkyl taurate; an amphoteric surface iactive agent; or anionic surface active agent containing an ethylene oxide chain as described in Belgian Pat. No. 650,004. r The antifoggant used in this invention having the repeating unit represented by general formula (1) has properties which differ from those of conventional antifoggants in that the antifoggant of this invention has a high molecular weight, and the antifoggant of this invention shows excellent antifogging :efiects with respect to silver halide emulsions.

Various s-triazine-type antifoggants (e.g., U.S. Pat. Nos.

lide when incorporating it in a silver halide emulsion layer, 2,476,536 and 2,948,612) have been known, but they were sitivity of the emulsion has 3 After aging of 2 days at 50 C. at 80% relative humidity.

containing a plurality of s-triazine rings as in the present invention.

it is well known that is is difficult to prevent the formation of fog in a photographic silver halide emulsion, when the senbeen increased by the combination of a sulfur sensitization, a gold sensitization and a reduction sensitization. The antifoggant of this invention can efi'ectively EXAMPLE 1 Each ofthe antifoggants (l)(5), (l3) (l6) and (17) was incorporated in a sulfurand gold-sensitized, high-speed gelatin-silver iodobromide negative emulsion, respectively, and the resulting silver halide emulsions were applied to a film base and dried. The light-sensitive films thus prepared were exposed on an NSG Il-type sensitometer (made by Tokyo Shibaura Electric Co.) and developed in a developer having the following composition for 8 minutes at 20 C:

N-methyl-p-aminophenol sulfate 2 g. Sodium Sulfite (anhydrous) 100 g Hydroquinone 5 g. Borax 2 Water to make 1 liter.

The photographic properties of the developed photographic films were examined and were compared with those of photographic films prepared and developed under same conditions except that the antifoggant of this invention was not included. The results of this experiment are shown in the following table.

Fresh After aging 3 Concentration (gJAg 1 mol) A B 2 A B None (control) 100 0. 14 75 0.27 Anti-Ioggant (1) 0.4 100 0.11 95 0.16 0.8 97 0.09 90 0.11 Anti-foggant (2) 0.4 98 0.10 98 0.14 0.8 95 0.07 92 0.11 Anti-foggant (3) 3.0 102 0. 12 94 0. 18 6.0 97 0.11 90 0.15 Anti-foggant (4) 0.8 98 0.09 93 0. 13 1.6 94 0.07 88 0.09 Anti-toggant (5) 0.8 98 0.12 96 0. 19 1.6 98 0.10 95 0.14 Anti-ioggant (13) 0.4 96 O. 10 90 0.12 0.8 90 0.06 88 0.09 Anti-Ioggant (16) 0.4 96 0.11 96 0.17 0.8 95 0.09 94 0.13 Anti-foggant (17) 0.4 101 0.13 90 0.16 0.8 97 0.09 90 '0. 11

1 Relative sensitivity. 2 F

As shown by the above results, the initial formation of fog was prevented by the antifoggants of this invention, and when the photographic film was developed after being aged for 2 days at C. and at a relative humidity of 80 percent, the formation of fog was also prevented, without a reduction in sensitivity.

EXAMPLE 2 Each of the antifoggants (6), (9), (l0), (l4) and (I5) was incorporated in a sulfur-reduction-and gold-sensitized highspeed gelatin-silver iodobromide X-ray emulsion, respectively, and the resulting silver halide emulsion was applied to a film base. The light-sensitive films thus prepared were exposed on an NSG ll-type sensitometer and developed for 6 minutes at 20 C. in a developer having the following composition:

N-methyl-p-aminophenol sulfate 2 g. Sodium sulfite (anhydrous) g. Hydroquinone 8 g. Sodium carbonate (anhydrous) 40 g.

Potassium bromide 2. Water to make 1 liter.

The properties of the developed film were compared with those of a photographic film treated under the same conditions with the exception that an antifoggant of this invention was not added. The results obtained are illustrated in the following table. From the results it is clear that the formation of fog was inhibited by the incorporation of the antifoggant of this invention when compared to the films wherein the antifoggant of this invention was not added.

Concentration Relative Fog (gJAg l mol) sensitivity None (control) 100 0.23 Antifoggant (6) 2.0 99 0.20 do 4.0 98 0.17 Antifoggant (9) 0.8 I00 021 do L6 96 0.!8 Antifoggant I0) 0.8 101 0.19 do L6 99 0. I 7 AntifogganHH) 0.8 96 0.17 do I .6 0.13 Antifoggant 15) 0.8 I04 0.20 do I .6 99 0.17

EXAMPLE 3 Sodium Pyrophosphate 20 g. Sodium sulfate 50 g. 37% Formaldehyde [7 ml. l0% sodium hydroxide l ml. Water to make 1 liter.

The light-sensitive films thus processed were washed with water for 4 minutes at 27 C. The films were then developed for 7 minutes at 27 C. in a developer having the following composition:

N-methyl-p-aminophenol sulfate 1 g.

Sodium Sulfite (anhydrous) 60 g. Hydroquinone l0 g. Sodium carbonate (mono-hydrate) 40 g. Potassium bromide 5 g. Potassium thiocyanate 1.5 g. 0.l% potassium iodide 5 ml. Water to make I liter.

The photographic properties of the thus developed photographic films were compared with those of a photographic film prepared and treated under the same conditions with the exception that an antifoggant of this invention was not added. The results obtained are shown in the following table and the results clearly show that fog-formation was prevented by the antifoggant of this invention.

Concentration Relative Fog (gJAg I mol) sensitivity None (control) I00 085 Antifoggant (l) 0.] I03 0.67 do 0.2 106 0.5l Antifogganl (2) 0.4 9 0.42 do 08 104 0.28 Antifoggant (7) [.0 "0 0.35 do 2.0 10! 0.25 Antifogganl (8) 20 Ill 0.24 do 4.0 99 0.!3

Each of the antifoggants (l l), (12), (i5) and (20) of this invention were incorporated in an aqueous 5 percent gelatin solution, respectively. A sulfurand gold-sensitized gelatino silver iodo-bromide emulsion for use as a reversal color photographic material was coated on a glass plate of about 200 sq. cm., and dried. Then, 5 ml. of the gelatin solution prepared, as above was coated on the silver halide emulsion layer and dried. The thus double-coated photographic plates were exposed on an NSG ll-type sensitometer and developed for 7 minutes at 27 C. in a developer having the same composition as in example 3.

The photographic properties of the photographic plates were compared with a plate which did not contain an antifoggant of this invention but which was otherwise identical. The results obtained were as follows:

Concentration Relative Fog (mg./ ml. of sensitivity 5% gelatin) None (control) I00 0.18 Antifoggant l l) 2.0 101 0.16 do 4.0 97 0.14 Antil'oggant [2) 20.0 9' 0.13 do 40.0 94 0.11 Antitoggant 15) 4.0 99 0.15

do 8.0 so o.|a Antiloggant (20) 4.0 100 0.15 do 8.0 95 0.12

It is clear from the results in the table that the formation of fog was prevented by incorporation of an antifoggant of this invention in a protective layer for a silver halide emulsion layer without substantially reducing the sensitivity of the silver halide emulsion.

EXAMPLE 5 Each of the antifoggants (l4), (l5), (l8) and (19) of this invention were incorporated in a sulfurand gold-sensitized gelatino-silver iodo-bromide emulsion for use as a reversal color photographic material. Each of the silver halide emulsions thus prepared was applied to a film base and dried. The photosensitive color films thus obtained were exposed and subjected to the following processings:

l. Prehardening 27' C. 3 minutes 2. Water rinsing 27 C. 4 minutes 3. Negative development 27' C. 7 minutes 4. Washing 27 C. 2 minutes 5. Reversal flash exposure 27 C.

6. Color development 27 C. 5 minutes 7. Water rinsing 27 C. 1 minute 8. Silver bleaching 27' C. 5 minutes 9. Fixing 27 C. 3 minutes 10 Water rinsing l i. Drying The compositions of the processing baths used in the processings were as follows:

The composition of the hardening bath and the negative developer were the same as those in example 3.

Color developing solution Sodium thiosulfate I00 g. Sodium sulfite l5 g. Water to make 1 liter.

The photographic properties of the color photographic films obtained were compared with those of a film treated under the same conditions but containing no antifoggant of this invention. The results obtained are shown in the following table, in which the maximum density was measured by using a blue filter after color development.

Concentration Maximum density (g-lAg l mol) None (control) 2.0 Antifoggant l4) 0.4 2.4 do 0.8 3.0 Antifoggant l5) 0.4 2.3 do 0.8 2.6 Antifoggant l9) [.0 2.3 do 2.0 2.6

As shown in the above table, when the antifoggant of this invention was incorporated in the silver halide emulsion, the maximum density of the color image obtained was greatly increased due to the reduction in the formation of fog during negative development.

EXAMPLE 6 The antifoggant 14) of this invention was added to samples of a sulfur and gold-sensitized gelatino-silver iodo-bromide emulsion for use as a negative color photographic material. 1- hydroxy-4-sulfo-2-n-octadecyl naphthamide was incorporated therein as a coupler by adding 20 parts by weight of an aqueous alkaline solution of the coupler l g. of the coupler per 1.4 mol of a 1N sodium hydroxide) to 100 parts by weight of the emulsion. The emulsion, after pH was adjusted to 7.0 with citric acid, was coated on a film base and dried.

The photosensitive color film thus obtained was exposed and developed using standard techniques in a color developer having the following composition:

N,N-diethyl-p-aminoaniline sulfate 2.0 g. Sodium sulfite 2.0 g. Sodium carbonate (monohydrate) 50.0 g. Hydroxylamine hydrochloride l.5 g. Potassium bromide L0 g. Water to make 1 liter.

The pH thereof was adjusted to 10.8 10.! using NaOH.

The photographic film thus developed was further processed in a silver bleaching bath having the composition set out below and in a fixing bath having the composition set out below in order to remove the undeveloped silver halide and reduced silver:

Bleaching solution Potassium l'erricyanide 100 g. Potassium bromide 20 g. Water to make I liter. Fixing solution Sodium thiosuifate 200 g. Sodium sulfite (anhydrous) 20 g. 28% acetic acid 45 g. Boric acid 7.5 g. Potassium alum 20 g. Water to make I liter.

After this treatment, the density was measured using a red filter. The results obtained were compared with those obtained when a photographic material prepared under the same conditions with the exception that the antifoggant of this invention was not added. The results obtained are illustrated in the following table.

Fresh After aging 3 Concentration (g./Ag 1 mol) A l B 2 A B None (control) 0.29 100 0.31 100 Anti-foggant (14) 0. 6 0.19 103 0. 16 103 1. 0 0. 13 100 0. 10 97 2. 0 0. 06 0.06 990 1 Cyan colored fog. 2 (Alien relative sensitivity. I B ter agingtor 2(1ays 51:50" O. and at 80% relative humidity.

EXAMPLE 7 A dispersion of a coupler, l-phenyl-3[3'(N-propyl-N-octylamidoJ-propioamidel-s-pyrazolone, was prepared by distion of sodium dodecylbenzene sulfonate and stirred at 80-90" C. l Parts by weight of the dispersion thus prepared was added to 100 parts of a sulfurand gold-sensitized gelatinosilver iodo-bromide emulsion. Antifoggant (2) of this inven- Magenta Concentration Magentarelative (gJAglmoie) colored fog sensitivity None (control) 0. 13 100 Antl-ioggant (2) 1.0 0. 0s 9a 2.0 0.06 87 As shown in the above table, the formation of the magentacolored fog was markedly prevented by the addition of the antifoggant, without substantial reduction in sensitivity.

EXAMPLE 8 To 100 parts by weight of a sulfurand gold-sensitized gelatino-silver chloro-bromide emulsion there was added 40 parts by weight of a percent aqueous alkaline solution of 3,5- dicarboxy- [(4-stearoyla.mido)benzoyl] acetanilide. Antifoggant (i) of this sion. After adjusting the pH to 8.0, the resulting emulsion was coated on a film base to a thickness of 6 microns.

To 100 parts by weight of a sulfur-sensitized red-sensitive gelatino-silver chlorobromide emulsion there was added parts by weight of a methanol solution of 0.25 percent 3-allyl- 6,7-benzo-3-ethyl- 1 ,5[2( i-ethyl-4-quinolinidene)ethylidene] a:thi zql notho xanme iodid and partsbuveighwf percent aqueous alkaline solution of l-hyd roxy-2-n-oc- To lOO parts by weight of a sulfur-sensitized green-sensitive gelatino-silver chloride emulsion there was added 5 parts by weight of a 0.05 percent methanol solution of 3,3-9-triethyl- 5 ,5 '-diphenyl-oxacarbocyanine rhodanide and 18 parts by weight of a 5 percent aqueous alkaline solution of l-[(3'- sulfo-4-phenoxy)benzene]-3-heptadecyl-S-pyrazolone. The pH was then adjusted to 7.5. After incorporating antifoggant face of the red-sensitive emulsion layer formed, described at a thickness of 6 microns.

as already Ihephqtosensitive colorfilm thus prepared was exposed and subjected to the following processing:

I. Color developing 20 C. it) minutes 2. Water rinsing 20" C. 2 minutes 3. Primary fixing 20 C. 5 minutes 4. Water rinsing 20 C. 5 minutes 5. Bleaching 20 C. 5 minutes 6. Secondary fixing 20 C. 5 minutes 7. Water rinsing 20 C. It) minutes The compositions of the color developer, fixing solutions, and the bleaching solution used in the above processing were the same as those described in example 6.

After processing, the densities thereof were measured by using a blue filter, a green filter and red filter respectively.

The photographic color film of this invention thus processed was compared with a control film which contained no antifoggant in accordance with this invention. The results of this comparison are shown in the following table.

Concentration of anti- Yellow Cyan Magenta ioggant (1) (g./ Ag one m0) A B 3 A B A B 0. 17 100 0. 18 100 0. 16 100 0. 14 103 0. 17 98 0. 16 108 0. 17 96 0. 12 100 0. 16 100 0. 16 101 0. 16 96 0. 11 92 0. 13 93 0. 11 86 0. 10 95 l Colored fog. 2 Relative sensitivity. N o'rE: (b) a blue-sensitive emulsion layer; (r) a red-sensitive emulsion layer; (g) a. green-sensitive emulsion layer.

As shown in the above table, the fog formation was remarkably reduced without substantially reducing the sensitivity.

When using other antifoggants which have the repeating units represented by general fonnula (1) other than the aforesaid antifoggants (1)( 20), almost identical results were obtained.

What is claimed is:

a compound having a repeating unit represented by the following formula said compound containing at least four s-triazine rings in its molecule, and the amount of said compound being from about 0.01 g. to about 50 g. per 1 mole of silver halide in said emulsion layer, wherein R represents a member selected from the group consisting of -OR, and -SR, where R and Reach represent a member selected from the group consisting of (i) a hydrogen atom; (ii) an alkyl group having from l-l2 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from 14 carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from 6-12 a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, an alkyl group having from l-4 carbon atoms,

an alkoxy group having from 1-4 carbon atoms, and a halogen atom; and unsubstituted cycloalkyl group, and a cycloalkyl group substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, each of said cycloalkyl groups having from 3-6 carbon atoms, an alkyl group having from l4 carbon atoms, an alkoxy group having from l-4 carbon atoms, and a halogen atom; and (iv) a pyridyl and a thiazolyl group; A represents a member selected from the group consisting of a polymethylene group having from 4-5 carbon atoms, and a polymethylene group having a heteroatomic group and forming a -6 membered ring together with a nitrogen atom; R R R and R each represent a member selected from the group consisting of a hydrogen atom, an alkyl group having from 14 carbon atoms and a hydroxyalkyl group; Y,, Y Y and Y each represent a member selected from the group consisting of a polymethylene group having from 2-12 carbon atoms, a polymethylene group having from 2-12 carbon atoms substituted by a member selected from the group consisting of an alkyl group having from l-4 carbon atoms and a hydroxyalkyl group having from l-4 carbon atoms,. an arylene group having 6-12 carbon atoms, an arylene group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l-4 carbon atoms, an alkoxy group having from l-4 carbon atoms and a halogen atom, a cycloalkylene group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l-4 carbon atoms, an alkoxy group having l-4 carbon atoms and a halogen atom; Z represents a member selected from the group consisting of an oxygen atom, a sulfonyl group and a hydrocarbon residual group having from l-2 carbon atoms; and k and m each represents 0 or 1.

2. A photographic silver halide light-sensitive element as claimed in claim 1 wherein R is a member selected from the group consisting of COONa N. NH-

t V 3. A photographic silver halide light-sensitive element as claimed in claim 1 wherein the atomic groups shown in said chemical formula as is a member selected from the group consisting of CH CH3 CH3 COONa 5. A photographic silver halide light-sensitive element comprising a support having thereon a light-sensitive silver halide emulsion layer and a gelatin layer adjacent thereto, said gelatin layer containing a compound having a repeating unit represented by the following formula:

sisting of R on, t

-OR, and where R and R each represent a member.

selected from the group consisting of (i) a hydrogen atom; (ii) an alkyl group having from l--] 2 carbon atoms, a hydroxyalkyl group, a sulfoalkyl group, a salt thereof, a carboxyalkyl group, a salt thereof, and an aralkyl group, each of said groups having from l4 carbon atoms in the main straight carbon chain thereof; (iii) an unsubstituted aryl group having from 6-12 carbon atoms, an aryl group having from 6-12 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, an alkyl group having from l4 carbon atoms,

' an alkoxy group having from 1-4 carbon atoms, and a halogen atom; an unsubstituted cycloalkyl group, and a cycloalkyl' group substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a sulfoxyl group, a salt thereof, a hydroxyl group, each of said cycloalkyl groups having from 3-6 carbon atoms, an alkyl group having from l4 carbon atoms, an alkoxy group having from l4 carbon atoms, and a halogen atom; and (iv) a pyridyl and a thiazolyl group; A represents a member selected from the group consisting of a polymethylene group having from 4-5 carbon atoms, and a polymethylene group having a heteroatomic group and forming a 5-6 membered ring together with a nitrogen atom; R R R and R each represent a member selected from the group consisting of a hydrogen atom, an alkyl group having from l4 carbon atoms and a hydroxyalkyl group; Y Y Y and Y each represent a member selected from the group consisting of a polymethylene group having from 2-12 carbon atoms, a polymethylene group having from 2-12 carbon atoms substituted by a member selected from the group consisting of an alkyl group having from l4 carbon atoms and a hydroxyalkyl group having from l4 carbon atoms, an arylene group having 6-l 2 carbon atoms, an arylene group having from 61 2 carbon atoms substituted by a member selected from the group consisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l4 carbon atoms, an alkoxy group having from l4 carbon atoms and a halogen atom, a cycloalkylene group having from 6-12 carbon atoms, and a cycloalkylene group having from 6-l2 carbon atoms substituted by a member selected from the group con-' sisting of a sulfo group, a salt thereof, a carboxyl group, a salt thereof, an alkyl group having from l4 carbon atoms, an alkoxy group having 14 carbon atoms and a halogen atom; Z represents a member selected from the group consisting of an oxygen atom, a sulfonyl group and a hydrocarbon residual group having from 1-2 carbon atoms; and k and m each represents 0 or 1.

6, A photographic silver halide light-sensitive element as claimed in claim 5 wherein R, is a member selected from the group consisting of -0H, 0 H1, 0 2 a, 4E:

8. A photographic silver halide light-sensitive element as claimed in claim 5, wherein said compound is a member selected from the group consisting of:

in g in the compound is: n.

Wherginjhe numbe of S- triazine 

2. A photographic silver halide light-sensitive element as claimed in claim 1 wherein R1 is a member selected from the group consisting of
 3. A photographic silver halide light-sensitive element as claimed in claim 1 wherein the atomic groups shown in said chemical formula as
 4. A photographic silver halide light-sensitive element as claimed in claim 1, wherein said compound is a member selected from the group consisting of: Wherein the number of S-triazine rings in the compound is:
 5. A photographic silver halide light-sensitive element comprising a support having thereon a light-sensitive silver halide emulsion layer and a gelatin layer adjacent thereto, said gelatin layer containing a compound having a repeating unit represented by the following formula:
 6. A photographic silver halide light-sensitive element as claimed in claim 5 wherein R1 is a member selected from the group consisting of
 7. A photographic silver halide light-sensitive element as claimed in claim 5 wherein the bridge between the atomic groups shown in said chemical formula as
 8. A photographic silver halide light-sensitive eleMent as claimed in claim 5, wherein said compound is a member selected from the group consisting of: 